CN109622002A - It is a kind of for improving the preparation method of the catalyst of BTX yield - Google Patents
It is a kind of for improving the preparation method of the catalyst of BTX yield Download PDFInfo
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- CN109622002A CN109622002A CN201811543532.4A CN201811543532A CN109622002A CN 109622002 A CN109622002 A CN 109622002A CN 201811543532 A CN201811543532 A CN 201811543532A CN 109622002 A CN109622002 A CN 109622002A
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- btx yield
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- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000126 substance Substances 0.000 claims abstract description 27
- 239000012528 membrane Substances 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 239000000499 gel Substances 0.000 claims description 32
- 239000013078 crystal Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 28
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000002808 molecular sieve Substances 0.000 claims description 19
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 11
- 239000000571 coke Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 229910021536 Zeolite Inorganic materials 0.000 claims description 10
- 239000003610 charcoal Substances 0.000 claims description 10
- 239000010457 zeolite Substances 0.000 claims description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- 238000005342 ion exchange Methods 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 239000001095 magnesium carbonate Substances 0.000 claims description 5
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 5
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000004523 catalytic cracking Methods 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 238000004939 coking Methods 0.000 abstract description 6
- 230000009471 action Effects 0.000 abstract description 5
- 229920002521 macromolecule Polymers 0.000 abstract description 4
- 150000003384 small molecules Chemical group 0.000 abstract description 3
- 238000005899 aromatization reaction Methods 0.000 abstract description 2
- 210000003850 cellular structure Anatomy 0.000 abstract description 2
- 238000005906 dihydroxylation reaction Methods 0.000 abstract description 2
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 41
- 239000003245 coal Substances 0.000 description 29
- 238000006555 catalytic reaction Methods 0.000 description 10
- 239000011269 tar Substances 0.000 description 10
- 230000006872 improvement Effects 0.000 description 9
- 238000012545 processing Methods 0.000 description 9
- 238000007233 catalytic pyrolysis Methods 0.000 description 8
- 238000005336 cracking Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 239000002028 Biomass Substances 0.000 description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 6
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 6
- 229910002651 NO3 Inorganic materials 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 238000000197 pyrolysis Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 102000053642 Catalytic RNA Human genes 0.000 description 1
- 108090000994 Catalytic RNA Proteins 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000002802 bituminous coal Substances 0.000 description 1
- 239000002864 coal component Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000045 pyrolysis gas chromatography Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 108091092562 ribozyme Proteins 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 230000010512 thermal transition Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/20—Carbon compounds
- C07C2527/232—Carbonates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
It is a kind of that active nuclear matter is added and is wrapped up in membrane substance gel solution, stirs evenly, air-dries at room temperature for improving the preparation method of the catalyst of BTX yield, it is calcined 4-6 hours at 490-510 DEG C after then drying, obtains catalyst.The quality of active nuclear matter and the volume ratio of package membrane substance gel solution are 1g:2-6mL.The present invention has the function of catalytic cracking to easy coking macromolecular compound and large-scale hydro carbons chain molecule by the wrap film of macroporous structure, the small molecules fragments to be formed are acted on through catalytic cracking can be more easily by the cellular structure of active nucleus, the reactions such as de- alkyl, aromatisation, dehydroxylation occur under the action of active nucleus acidic site, to improve the selectivity of BTX.
Description
Technical field
The invention belongs to the technical fields of energy deep processing, are related to a kind of for improving the preparation of the catalyst of BTX yield
Method.
Background technique
In view of the energy national conditions in China, coal will occupy for a long time absolute leading position in non-renewable energy Supply Structure, greatly
Power Development of Coal chemical industrial chain utilizes the integration of coal resources and has important practical significance.Pyrolysis of coal is coal in thermal transition benefit
With process at first with necessary reaction step, the semicoke of the coal gas of gas, the tar of liquid, solid can be obtained by pyrolysis of coal
Three kinds of products.Wherein BTX (benzene,toluene,xylene) can be the downstream of coal chemical industry as the light aromatics in pyrolytic tar product
Extend and good basic material is provided.In addition to this, biomass, heavy oil, plastics, rubber etc. are used to be pyrolyzed that BTX can also be produced.
Synthetic rubber, plastics, synthetic fibers such as can be produced with BTX, they are basic bulk chemicals.However existing coal, biology
Have to be solved there is also certain problem in the pyrolytic process such as matter, if tar yield is too low, the high value added product in oil product is (such as
BTX) to be improved, heavy component, condensed-nuclei aromatics content height in tar etc..In recent years, catalyst is pyrolyzed in coal, biomass etc.
In be widely used.By catalysis, the converting rate of coal or biomass etc. on the one hand can be improved, reduce reaction temperature
Degree, makes pyrolysis operations mild condition；On the other hand it can also regulate and control composition and the distribution of thermal decomposition product, realize coal, biology
Matter etc. is converted to the orientation of high level chemicals.
Chinese invention CN105670670A loads nanometer iron-series catalyst by the raw coal of preparation energy efficient catalytic pyrolysis of coal
And in selection pyrolytic process catalyst and raw coal appropriate proportioning, it is anti-in fixed bed that bituminous coal with catalyst is formed by mixture
It answers in device and is pyrolyzed, to improve pyrolytic tar yield, and significantly improve the quality of pyrolytic tar.
Metal nitrate, molecular sieve, deionized water are prepared into mixed solution, through roasting by Chinese invention CN105536852A
The catalyst that regulation thermal decomposition product composition and distribution can be obtained after burning increases considerably when being pyrolyzed jet coal with the catalyst
Pyrolytic tar yield, and the selectivity of aromatic hydrocarbons and phenol improves in pyrolytic tar, alcohols material is substantially reduced.
Above-mentioned document is the research that related scholar is done in terms of the catalytic pyrolysis of coal, these methods improve coke really
The quality of oil, also increases the yield of related high value added product.But some problems are still had, substantially all such as the above method
Belong to it is one stage catalyzing, in this process the hydrocarbon compound of inertia and the macromolecular compound and long-chain that are easy to coking be difficult into
The effective Collection utilization of row.
It is proposed in Chinese invention CN106010617A through two-step catalysis method (i.e. selective catalysis and shape selective catalysis)
Improve the yield and selectivity of aromatic hydrocarbon product in biomass, this method can effectively reduce the coking and deactivation speed of catalyst
Rate extends the service life of catalyst.Since the interval time being catalyzed twice in this method is too long, institute holds very much in the process in this way
It is also easy to produce carbon distribution.
Summary of the invention
The purpose of the present invention is to provide a kind of for improving the preparation method of the catalyst of BTX yield, this method preparation
Catalyst, in the wrap film with Catalytic Cracking Performance and under the total catalytic action of shape selective catalysis active nucleus, by changing
Become the pore structure of active nucleus, the thickness of surface acidity and wrap film, density etc. and shape selective catalysis carried out to product, so improve coal,
BTX yield in the pyrolytic tars product such as biomass.
To achieve the above object, the present invention adopts the following technical scheme that:
It is a kind of for improving the preparation method of the catalyst of BTX yield, by active nuclear matter be added package membrane substance gel
It in solution, stirs evenly, air-dries at room temperature, calcined 4-6 hours at 490-510 DEG C after then drying, obtain catalyst.
A further improvement of the present invention lies in that the quality of active nuclear matter and the volume ratio of package membrane substance gel solution are
1g:2-6mL.
A further improvement of the present invention lies in that active nuclear matter is HZSM-5 molecular sieve, active carbon, coke, natural zeolite
Or charcoal；Active nuclear matter is calcined under an inert atmosphere when being active carbon, coke or charcoal.
A further improvement of the present invention lies in that HZSM-5 molecular sieve is made by following procedure: by active crystal seed
It is added in aluminosilicate gels solution, after mixing evenly, closed 2.5~3.5h of crystallization, naturally cools at 205~215 DEG C
Room temperature, dry after centrifuge washing, 550 DEG C of calcining 4-6h, ion exchange three times, obtains HZSM-5 molecular sieve after 550 DEG C of calcining 4h.
A further improvement of the present invention lies in that the quality of active crystal seed is active crystal seed and alumino-silicate
The 4~10% of gel solution gross mass.
A further improvement of the present invention lies in that the detailed process of ion exchange are as follows: weigh the NH of 24g4NO3It is dissolved in 300mL's
Deionized water is configured to the solution of 1mol/L, by catalyst and solution with quality: container is added in the ratio that volume is 1g:30mL
In, 80 DEG C are warming up to, 2h, filtering and washing are condensed back.
A further improvement of the present invention lies in that package membrane substance is Al2O3、CaCO3Or MgCO3。
A further improvement of the present invention lies in that mixing time 3-5h, air-dry time is 24 hours.
A further improvement of the present invention lies in that dry temperature is 105 DEG C, the time is 5-7 hours.
A further improvement of the present invention lies in that further including the modification to catalyst, detailed process are as follows: 5g catalyst to be added
In the NaOH solutions for being 7-9 to 100mL pH value, 80 DEG C of stirring 0.5h are then heated to, are then washed through deionized water, filtered,
After drying, 4h is calcined at 550 DEG C.
Compared with prior art, the beneficial effects of the present invention are:
Compared to traditional catalyst, the present invention is using active nuclear matter, using the method for class collosol and gel in active nucleus
Outer surface formed wrap film, be prepared ground spheric catalyst.The catalyst using the substance with Catalytic Cracking Performance as
Wrap film, using the substance with shape selective catalysis as activity core, catalytic cracking effect catalytic cracking fenestra road be much larger than in be indecisive and changeable
Property nucleopore road.There is catalysis to easy coking macromolecular compound and large-scale hydro carbons chain molecule by the wrap film of macroporous structure
The effect of cracking, the small molecules fragments to be formed are acted on through catalytic cracking can be more easily by the cellular structure of active nucleus, in work
Property ribozyme position under the action of the reactions such as de- alkyl, aromatisation, dehydroxylation occur, to improve the selectivity of BTX.
Further, the existing package membrane substance (Al of catalyst2O3、CaCO3、MgCO3) to pyrolytic tars such as coal, biomass
The catalytic cracking effect of generated easy coking macromolecular compound and large-scale hydro carbons chain molecule in product, and active core
(ZSM-5, active carbon, coke, natural zeolite, charcoal) selectively produces the shape selective catalysis effect of BTX, and in catalytic process
It is not likely to produce carbon distribution.
Further, catalyst is modified, the present invention is using the corrasion of alkaline matter sodium hydroxide to novel
Catalyst is modified, and the yield of BTX can be further improved.
Detailed description of the invention
Fig. 1 is influence schematic diagram of the variation of Silicalite-1 crystal seeds additional amount in catalyst to BTX yield；
Fig. 2 is influence schematic diagram of the ratio variation to BTX yield in catalyst between HZSM-5 mass and volume；
Fig. 3 is influence of the modified new catalyst to BTX yield；
Fig. 4 is influence schematic diagram (the wrap film Al by changing active nucleus to BTX yield2O3)；
Fig. 5 is influence schematic diagram (the wrap film CaCO by changing active nucleus to BTX yield3)；
Fig. 6 is influence schematic diagram (the wrap film MgCO by changing active nucleus to BTX yield3)；
Specific embodiment
By specific embodiment, the present invention is described in detail with reference to the accompanying drawing.
It is big that the catalytic cracking effect of the outer layer of catalyst of the present invention will be difficult to before the easy coking entered in active nucleus duct
Molecular compound and large-scale hydro carbons chain molecule interrupt, and enter more small molecule segments among duct, select in active nucleus
The yield of BTX is significantly improved under the action of the catalysis of selecting property.
Catalyst of the invention in use, sample preparation and pyrolytic reaction.
(1) preparation of sample
Selected coal is the eastern coal of mind in the present invention, belongs to the lower-grade metamorphic bituminous one kind in northern Shensi.Refreshing east coal component is shown in Table 1,
Lump coal obtains granularity < 0.075mm coal sample after jaw crusher and ball mill crush and screen, in 105 DEG C of vacuum ovens
Middle drying is fitted into spare in brown bottle afterwards for 24 hours.
The Industrial Analysis and elemental analysis of the eastern coal of 1 mind of table
* minusing obtains
(2) pyrolytic reaction
Sample is analyzed using pyrolysis gas chromatograph combined instrument (Py-GC/MS), wherein the effect of cracking instrument (Py) is
Fast catalytic pyrolysis is carried out to sample, gas chromatograph (GC/MS) carries out on-line analysis to product.
Embodiment 1
The TPAOH (tetrapropylammonium hydroxide) for weighing the NaOH and 8.9478g of 0.08g is uniformly mixed, and distilled water is added
Mixed solution is made in 100mL.The TEOS (ethyl orthosilicate) of 52.083g is added in above-mentioned mixed solution, distilled water is added
98mL.The system is stirred at room temperature 24 hours.Mixture is transferred in conical flask, hydrothermal solution flows back under 363K (90 DEG C)
For 24 hours, Silicalite-1 crystal seeds are obtained.
Silicalite-1 crystal seeds addition in above-mentioned steps without any processing is filled into 70mL aluminosilicate gels
Solution (Al2O3: SiO2: Na2O:H2O=1:100:30:4200 in 100mL polytetrafluoroethyllining lining), wherein
The quality of Silicalite-1 crystal seeds is the gross mass of Silicalite-1 crystal seeds and aluminosilicate gels solution
4%, it stirs evenly, in 210 DEG C of crystallization 2h, naturally cools to room temperature, 100 DEG C of centrifuge washing are dried overnight, and 550 DEG C of calcining 6h are gone
Except template agent.Use the NH of 0.1mol/L4NO3Ion exchange three times, obtains HZSM-5 after 550 DEG C of calcining 4h under the conditions of 80 DEG C
Molecular sieve.Wherein, the detailed process of ion exchange are as follows: weigh the NH of 24g4NO3The deionized water for being dissolved in 300mL is configured to 1mol/
The solution of L, by catalyst and solution with quality: volume is that the ratio of 1g:30mL is added to the container, and is warming up to 80 DEG C, is condensed back to
Flow 2h, filtering and washing.
By quality: it is molten gel aluminum hydroxide to be added in HZSM-5 molecular sieve obtained in above-mentioned steps by volume=1g:2mL
In liquid, 4h is stirred, is air-dried 24 hours at room temperature, is then put in baking oven drying 6 hours at 105 DEG C, then be placed in high temperature furnace
In calcine at 500 DEG C and go within 4 hours moisture removal to get to catalyst.
Using Py/GC-MS, the catalyst being prepared is subjected to catalytic pyrolysis to refreshing eastern coal, cracking temperature is set as 600
DEG C, the mass ratio of raw material and catalyst is 1:2, is evaluated the content of BTX, evaluation result is shown in Fig. 1.As can be seen that in reality
Under the action of the catalyst for applying example 1, BTX yield has apparent increase.Compared to the catalytic effect of business ZSM-5, the production of BTX
Rate increases 9.35%.
Embodiment 2
Using without the Silicalite-1 crystal seeds of any processing, removing Silicalite-1 crystal seeds in embodiment 1
Quality be Silicalite-1 crystal seeds and aluminosilicate gels solution gross mass 6% outside, remaining experimental method is same
Embodiment 1.
Embodiment 3
Using without the Silicalite-1 crystal seeds of any processing, removing Silicalite-1 crystal seeds in embodiment 1
Quality be Silicalite-1 crystal seeds and aluminosilicate gels solution gross mass 8% outside, remaining experimental method is same
Embodiment 1.
Embodiment 4
Using without the Silicalite-1 crystal seeds of any processing, removing Silicalite-1 crystal seeds in embodiment 1
Quality be Silicalite-1 crystal seeds and aluminosilicate gels solution gross mass 10% outside, remaining experimental method is same
Embodiment 1.
Referring to Fig. 1, when Silicalite-1 Seed charge is 4%, the catalytic effect of catalyst prepared by the present invention
Preferably, BTX yield can reach 65.69% at this time.
Embodiment 5
Using in embodiment 1 without the Silicalite-1 crystal seeds of any processing, except pressing quality: volume=1g:3mL,
Except HZSM-5 molecular sieve obtained in above-mentioned steps is added in gel aluminum hydroxide solution, the same embodiment of remaining experimental method
1。
Embodiment 6
Using in embodiment 1 without the Silicalite-1 crystal seeds of any processing, except pressing quality: volume=1g:4mL,
Except HZSM-5 molecular sieve obtained in above-mentioned steps is added in gel aluminum hydroxide solution, the same embodiment of remaining experimental method
1。
Embodiment 7
Using in embodiment 1 without the Silicalite-1 crystal seeds of any processing, except pressing quality: volume=1g:5mL,
Except HZSM-5 molecular sieve obtained in above-mentioned steps is added in gel aluminum hydroxide solution, the same embodiment of remaining experimental method
1。
Embodiment 8
Using in embodiment 1 without the Silicalite-1 crystal seeds of any processing, except pressing quality: volume=1g:6mL,
Except HZSM-5 molecular sieve obtained in above-mentioned steps is added in gel aluminum hydroxide solution, the same embodiment of remaining experimental method
1。
Referring to fig. 2, when quality and volume ratio are 1g:5mL, the catalytic effect of catalyst is best, and BTX yield is reachable at this time
To 69.98%.
Embodiment 9
5g catalyst molecule as obtained in embodiment 1 sieve original powder is taken to add in the NaOH solution that people's 100mLpH value is 7-9,
It is allowed to warm to 80 DEG C of stirring 0.5h.The sample handled well is washed by deionized water, is filtered, after drying, is calcined at 550 DEG C
4h obtains modified catalyst.
Using Py/GC-MS, the modified catalyst of preparation is subjected to catalytic pyrolysis, cracking temperature setting to refreshing eastern coal
It is 600 DEG C, raw material (mind east coal) and the mass ratio of catalyst are 1:2, are evaluated the content of BTX, evaluation result is shown in Fig. 3.
As can be seen that BTX yield has apparent increase under the action of modification.Compared to the unmodified catalyst in embodiment 1,
The yield of the BTX of modified catalyst increases 4.07%.
Embodiment 10
Prepared aluminum trichloride solution is first added in three-necked flask, and loads onto blender, is put in thermostat and heats up
40 DEG C are heated to, is quickly poured into ammonium hydroxide under stiring, is adjusted between pH value 8-9, is stopped plus ammonium hydroxide, continuing to stir will after 30min
Active carbon presses quality: volume=1g:2mL is added in gel aluminum hydroxide solution, stirs 4h, 24 hours air-dried at room temperature, so
After be put in baking oven at 105 DEG C 6 hours dry, then be placed in high temperature furnace to calcine 4 hours at 500 DEG C and remove moisture removal to get arriving
New catalyst.Likewise, active carbon is replaced with coke, natural zeolite and charcoal, calcines make under an inert atmosphere
Obtain corresponding new catalyst.
Using Py/GC-MS, the new catalyst being prepared is subjected to catalytic pyrolysis, cracking temperature setting to refreshing eastern coal
It is 600 DEG C, the mass ratio of raw material and catalyst is 1:2, is evaluated the content of BTX, evaluation result is shown in Fig. 4.As can be seen that
When wrap film is Al2O3, when active nuclear matter is ZSM-5, BTX yield highest can reach 65.69%.
Embodiment 11
By obtained HZSM-5 (active carbon, coke, natural zeolite, charcoal) by quality: volume=1g:2mL is added to
It is placed in the three-necked flask for being placed with calcium chloride solution, three-necked flask is added in sodium carbonate liquor under stiring, is stirred under room temperature
4h, stands 30min, then washing, filtering are put in baking oven drying 6 hours at 105 DEG C, then are placed in high temperature furnace at 500 DEG C
Calcining removes moisture removal for 4 hours to get new catalyst is arrived.Likewise, HZSM-5 is replaced with active carbon, coke, natural zeolite
Or charcoal, corresponding new catalyst is made under an inert atmosphere.
Using Py/GC-MS, the new catalyst being prepared is subjected to catalytic pyrolysis, cracking temperature setting to refreshing eastern coal
It is 600 DEG C, the mass ratio of raw material and catalyst is 1:2, is evaluated the content of BTX, evaluation result is shown in Fig. 5.As can be seen that
When wrap film is CaCO3, when active nuclear matter is ZSM-5, BTX yield highest can reach 50.21%.
Embodiment 12
Prepared aqueous soda solution is added in three-necked flask, is put in thermostat and is heated to 75 DEG C, by what is obtained
Magnesium chloride solution is added by a certain percentage (quality: volume=1:2) in HZSM-5 (active carbon, coke, natural zeolite, charcoal)
In, the solution is added dropwise in sodium carbonate liquor with dropper, after reacting 30min, liquid-solid mixture is stood into 30min, is washed
It washs, filters, product is put into and dries 6h in baking oven at 105 DEG C, then is placed in high temperature furnace to calcine 4 hours at 500 DEG C and goes to remove water
Divide to get new catalyst is arrived.Likewise, HZSM-5 is replaced with into one of active carbon, coke, natural zeolite, charcoal,
Corresponding new catalyst is made under an inert atmosphere.
Using Py/GC-MS, the new catalyst being prepared is subjected to catalytic pyrolysis, cracking temperature setting to refreshing eastern coal
It is 600 DEG C, the mass ratio of raw material and catalyst is 1:2, is evaluated the content of BTX, evaluation result is shown in Fig. 6.As can be seen that
When wrap film is MgCO3, when active nuclear matter is ZSM-5, BTX yield highest can reach 50.08%.
Embodiment 13
Active nuclear matter is added in package membrane substance gel solution, 5h is stirred, air-dries 24 hours, then exists at room temperature
At 105 DEG C after drying 7 hours, is calcined 6 hours at 490 DEG C, obtain catalyst.
The quality of active nuclear matter and the volume ratio of package membrane substance gel solution are 1g:6mL.
Active nuclear matter is HZSM-5 molecular sieve；
HZSM-5 molecular sieve is made by following procedure: active crystal seed is added in aluminosilicate gels solution,
After mixing evenly, the closed crystallization 3.5h at 205 DEG C naturally cools to room temperature, dries after centrifuge washing, 550 DEG C of calcining 6h, from
Son exchange three times, obtains HZSM-5 molecular sieve after 550 DEG C of calcining 4h.
The quality of active crystal seed is the 4% of active crystal seed and aluminosilicate gels solution gross mass.
The detailed process of ion exchange are as follows: weigh the NH of 24g4NO3The deionized water for being dissolved in 300mL is configured to 1mol/L's
Solution, by catalyst and solution with quality: volume is that the ratio of 1g:30mL is added in container, is warming up to 80 DEG C, is condensed back
2h, filtering and washing.
Package membrane substance is Al2O3。
Embodiment 14
Active nuclear matter is added in package membrane substance gel solution, 3h is stirred, air-dries 24 hours, then exists at room temperature
At 105 DEG C after drying 5 hours, is calcined 4 hours at 510 DEG C, obtain catalyst.
The quality of active nuclear matter and the volume ratio of package membrane substance gel solution are 1g:2mL.
Active nuclear matter is HZSM-5 molecular sieve.
HZSM-5 molecular sieve is made by following procedure: active crystal seed is added in aluminosilicate gels solution,
After mixing evenly, the closed crystallization 2.5h at 215 DEG C naturally cools to room temperature, dries after centrifuge washing, 550 DEG C of calcining 4h, from
Son exchange three times, obtains HZSM-5 molecular sieve after 550 DEG C of calcining 4h.
The quality of active crystal seed be active crystal seed and aluminosilicate gels solution gross mass 4~
10%.
The detailed process of ion exchange are as follows: weigh the NH of 24g4NO3The deionized water for being dissolved in 300mL is configured to 1mol/L's
Solution, by catalyst and solution with quality: volume is that the ratio of 1g:30mL is added in container, is warming up to 80 DEG C, is condensed back
2h, filtering and washing.
Package membrane substance is CaCO3。
Embodiment 15
Active nuclear matter is added in package membrane substance gel solution, 5h is stirred, air-dries 24 hours, then exists at room temperature
At 105 DEG C after drying 6 hours, is calcined 5 hours at 500 DEG C under an inert atmosphere, obtain catalyst.
The quality of active nuclear matter and the volume ratio of package membrane substance gel solution are 1g:3mL.
Active nuclear matter is natural zeolite；Package membrane substance is MgCO3。
Modification to above-mentioned catalyst, detailed process are as follows: it is molten that 5g catalyst is added to the NaOH that 100mL pH value is 7
In liquid, 80 DEG C of stirring 0.5h are then heated to, are then washed through deionized water, filtered, after drying, calcine 4h at 550 DEG C.
Embodiment 16
Active nuclear matter is added in package membrane substance gel solution, 4h is stirred, air-dries 24 hours, then exists at room temperature
At 105 DEG C after drying 5-7 hours, is calcined 5 hours at 510 DEG C under an inert atmosphere, obtain catalyst.
The quality of active nuclear matter and the volume ratio of package membrane substance gel solution are 1g:6mL.
Active nuclear matter is natural zeolite；Package membrane substance is Al2O3。
Modification to above-mentioned catalyst, detailed process are as follows: it is molten that 5g catalyst is added to the NaOH that 100mL pH value is 9
In liquid, 80 DEG C of stirring 0.5h are then heated to, are then washed through deionized water, filtered, after drying, calcine 4h at 550 DEG C.
Claims (10)
1. a kind of for improving the preparation method of the catalyst of BTX yield, which is characterized in that wrap film is added in active nuclear matter
It in substance gel solution, stirs evenly, air-dries at room temperature, calcine 4-6 hours, obtain at 490-510 DEG C after then drying
Catalyst.
2. according to claim 1 a kind of for improving the preparation method of the catalyst of BTX yield, which is characterized in that living
Property nuclear matter quality and package membrane substance gel solution volume ratio be 1g:2-6mL.
3. according to claim 1 a kind of for improving the preparation method of the catalyst of BTX yield, which is characterized in that living
Property nuclear matter be HZSM-5 molecular sieve, active carbon, coke, natural zeolite or charcoal；Active nuclear matter be active carbon, coke or
It is calcined under an inert atmosphere when charcoal.
4. according to claim 1 a kind of for improving the preparation method of the catalyst of BTX yield, which is characterized in that
HZSM-5 molecular sieve is made by following procedure: active crystal seed being added in aluminosilicate gels solution, is stirred evenly
Afterwards, closed 2.5~3.5h of crystallization at 205~215 DEG C naturally cools to room temperature, dry, 550 DEG C of calcining 4- after centrifuge washing
6h, ion exchange three times, obtain HZSM-5 molecular sieve after 550 DEG C of calcining 4h.
5. according to claim 4 a kind of for improving the preparation method of the catalyst of BTX yield, which is characterized in that tool
The quality of active crystal seed is the 4~10% of active crystal seed and aluminosilicate gels solution gross mass.
6. according to claim 4 a kind of for improving the preparation method of the catalyst of BTX yield, which is characterized in that from
The detailed process of son exchange are as follows: weigh the NH of 24g4NO3The deionized water for being dissolved in 300mL is configured to the solution of 1mol/L, will be catalyzed
Agent and solution are with quality: volume is that the ratio of 1g:30mL is added to the container, and is warming up to 80 DEG C, is condensed back 2h, filtering and washing.
7. according to claim 1 a kind of for improving the preparation method of the catalyst of BTX yield, which is characterized in that packet
Wrapping substance is Al2O3、CaCO3Or MgCO3。
8. according to claim 1 a kind of for improving the preparation method of the catalyst of BTX yield, which is characterized in that stir
Mixing the time is 3-5h, and air-dry time is 24 hours.
9. according to claim 1 a kind of for improving the preparation method of the catalyst of BTX yield, which is characterized in that dry
Dry temperature is 105 DEG C, and the time is 5-7 hours.
10. according to claim 1 a kind of for improving the preparation method of the catalyst of BTX yield, which is characterized in that also
Including the modification to catalyst, detailed process are as follows: be added to 5g catalyst in the NaOH solution that 100mL pH value is 7-9, so
After be warming up to 80 DEG C of stirring 0.5h, then washed through deionized water, filter, after drying, calcine 4h at 550 DEG C.
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